Process for breaking petroleum emulsions



April 17, 1951 M. DE GROOTE arm. 2,54

PROCESS FOR BREAKING PETROLEUM summons Filed Sept. 28, 1949 2 Sheets-Sheet l Melvin DeGroote Arthur F. winel Owen Hpei'i'ingill A c C H 0 HYDROPHOBIC INVENTORS 3 6 REACTANT ATTORNEYS F April 1951 M. DE GROOTE ETAL 2,549,43

PROCESS FOR BREAKING PETROLEUM EMULSIONS Filed Sept. 28, 1949 2 Sheets-She'et 2 I007, FIG3 CBHSO ALPHA ERPINEOL Melvin De Groore Ari'hur F. Wiri'el Owen H. PeHingill INVENTORS ATTORNEYS Patented Apr. 17, 1951 anus T F g C PROCESS FGR BREAKING PETRGLEUM EMULSIONS Application September 28, 1949, Serial No. 118,411

7 Claims.

This invention relates to processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions.

Complementary to the above aspect of the in vention herein disclosed is our companion invent-ion concerned with the new chemical products or compounds used as the demulsifying agents in said aforementioned processes or procedures, as well as the application of such chemical compounds, products, or the like, in various other arts and industries, along with the method for manufacturing said new chemical products or compounds which are of outstanding value in demulsification. See our co-pending application, Serial No. 118,412, filed September 28, 1949.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occiuring Water or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or Weak brines. Controlled emulsification and subsequent demulsification, under the conditions just mentioned, are of significant value in removing impurities, particularly inorganic salts from pipeline oil.

Demulsification as contemplated in the present application includes the preventive step of commingling the demulsifier with the aqueous compound which would or might subsequentl become either phase of the emulsion in the absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.

Briefly stated, the present process is concerned with the brealnng of petroleum emulsions by means of certain glycol ethers of alpha-terpineol, and particularly in the form of cogeneric mixtures, as hereinafter described. These products are obtained by treatment of alpha-terpineol with glycide, ethylene oxide and propylene oxide within the limits and manner hereinafter specified.

It is Well known that a variety of compounds containing a reactive hydrogen atom, i. e., a hydrogen atom attached to oxygen, nitrogen, or sulphur, will react with alkylene oxides, particularly ethylene oxide, or propylene oxide, and sometimes perhaps glycide, to yield the corresponding glycol or polyglycol derivative. Such oxalkylated derivatives are readily prepared from chemical compounds in which the hydrogen atom is directly attached to oxygen, and particularly in the case of alcohols or phenols such as aliphatic alcohols, phenols, alkylaryl alcohols, alicyclic alcohols, phenoxyalkanols, substituted phenoxyalkanols, etc. Generally speaking, it has been found advantageous to react a water-insoluble hydroxylated material, having 8 carbon atoms or more, with an alkylene oxide 50 as to introduce water solubility, or at least significant or distinct hydrophile character, with the result that the derivative so obtained has surface-active properties.

Examples of suitable reactants of this type include octyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, octadecyl alcohol, butylphenol, propylphenol, propylcresol, hexylphenol, octylphenol, nonylphenol, and cardanol, as Well as the corresponding alicyclic alcohols obtained by the hydrogenation of the aforementioned phenols. It has been suggested that at least some of such materials be used in the resolution of petroleum emulsions. As far as We are aware, none of such materials represent products which are acceptable in demulsification today from a competitive standpoint. In the majority of'cases such products are apt to be one-sixth, one-fifth, onefourth, or one-third as good as available demulsifying agents on the same percentage-of-activematerial basis, or same cost basis.

We have discovered a very few exceptions to the above general situation. For example, we have discovered if one treats alpha-terpineol with glycide, ethylene oxide and propylene oxide so as to yield a cogeneric mixture of glycol ethers, that such mixed derivative has unusual properties, provided the composition lies within a certain range, as hereinafter specified. A specific exemplification of this range is the product ob-- tained by treating one mole of alpha-terpineol with one mole of glycide, then with 15 moles of propylene oxide, and then with 18 moles of ethylene oxide. Similarly, one may treat the glycidetreated alpha-terpineol with the 18 moles of ethylene oxide first and then with the 15 moles of propylene oxide next.

In subsequent paragraphs from time to time reference is made to compounds or cogeneric mixtures. At first glance it may appear that such language is indefinite, and perhaps contradictory. It is the intention at the moment only to point out that there is no inconsistency in such description and that subsequently there will be a complete explanation of why such designation is entirely proper.

As has been pointed out previously the present invention is concerned with certain reaction products or cogeneric mixtures obtained from four reactants or components combined in certain specific proportions as hereinafter described in detail. There is no difficulty in setting forth in graphic form a somewhat similar mixture obtained from three components instead of four, i. e., from terpineol, for example, either alpha or beta, and ethylene oxide and propylene oxide as distinguished from a quaternary mixture employing the same three reactants and also glycide in addition.

Our (so-pending applications, Serial Nos. 109,791, through 109,797, inclusive, all filed August 11, 1941, and Serial No. 110,332, filed August 1.5, 1949, described tertiary mixtures using the conventional triangular graph. The transition from a triangular graph to what would normally be a space model (a regular tetrahedron) followed by subsequent modification so as to transform a three-dimensional model within certain limitations to a two-dimensional plane, presents a certain amount of detailed text and for this reason what is said subsequently will appear in certain parts or divisions, as follows:

Part 1 is concerned with the importance of glycide in affecting the structure of the derivatives, and the method of presentation herein employed with reference to Figures 1, 2, 3 and 4.

Part 2 is in essence the verbatim text as it appears in our co-pending applications, Serial Nos. 109,791, 109,792, and 109,793, all filed August 11, 1949, and Serial No. 110,332, filed August 15, 1949, and discusses the preparation of a tertiary mixture from a terpineol, ethylene oxide, and propylene oxide, and discusses its presentation in the form of a triangular graph, together with detailed information as to the chemistry and structures involve-d.

Part 3 is concerned with the preparation of the compounds employing four components of four reactants and in its simplest form perhaps btainable by treating the tertiary mixtures of Part 2 preceding with glycide within the range hereinafter specified, i. e., that the final reaction product, or cogeneric mixtures, contain at least 2 and not more than 25 of glycide.

Part 4 consists of tables in which the limiting values are set forth in detail in tabular form so that the invention is set forth with particularity PART 1 The present invention is concerned with a cogeneric mixture which is the end product of a reaction or reactions involving 4 reactants. Assuming completeness of reaction and based on a mathematical average, the final product is characterized most conveniently in terms of the 4 component reactants. This phase of the invention is described elsewhere in greater detail.

In representing a mixture or an end product derived from 2 components or 3 components, there is no difiiculty as far as using the plane surface of an ordinary printed sheet. For example, a 3- component system is usually represented by a triangle in which the apexes represent of each component and any mixture or reaction product in terms of the 3 components is represented by a point in the triangular area in which the composition is indicated by perpendiculars from such point to the sides. Such representation is employed, for example, in co-pending applications of Melvin De Groote, Arthur F. Wirtel and Owen H. Pettingill, Serial Nos. 109,791, 109,792, 109,793, 109,794, 109,795, 109,796, and 109,797, all filed August 11, 1949, and Serial No. 110,332, filed August 15, 1949.

Chemists and physicists ordinarily characterize a 4-component system by using a solid, i. e., a regular tetrahedron. In this particular presentation each point or apex represents 100% of each of the 4 components, each of the 6 edges represents a line or binary mixture of the 2 components represented by the apexes or points at the end of the line or edge. Each of the 4 triangles or faces represent a tertiary mixture of the 3 components represented by the 3 corners or apexes and obviously signify the complete absence of the 4th component indicated by the corner or apex opposite the triangular face.

However, as soon as one moves to a point within the regular tetrahedron one has definitely characterized and specified a 4-component mixture in which the 4 components add up to 100%.

The invention will be described by reference to the accompanying drawings, which illustrate, in conventional graphical form, compositions used in accordance with the invention in terms of the four components. In the drawings, Figure 1 is a conventional tetrahedron, distorted somewhat for clarity to illustrate how a point within it fixes the proportions of the four constituents; Figure 2 is such a tetrahedron used to illustrate how, having a fixed amount of one constituent the other three may be determined by reference to a planar figure, of the type shown in Figure 3; and Figure 4 is another conventional tetrahedron in which a trapezoidal area is blocked out which defines the scope of the invention.

In accompanying Figure 1 an attempt is made to illustrate this system of representation visibly in a plane surface. For sake of convenience one need only consider a regular tetrahedron resting on one face or triangular surface. If somewhere towards the middle of such tetrahedron one places a plane parallel to the base or" the tetrahedron one again obtains an equilateral triangle which, of course, is reduced in size compared with the equilateral triangle which is the bottom of the regular tetrahedron. In Figure l the tetrahedron may be considered as formed by some transparent material and for convenience the new tetrahedron formed by the passage of the horizontal plane is, of course, a regular tetrahedron also. For convenience, one can consider that he is looking directly at this tetrahedron which is shown somewhat distorted for purpose of convenience, and in the smaller regular tetrahedron the apexes are T, U, V and D. The lines are TU, VU, TV and VD. The four equilateral triangles are TVD, UVD, TUV and TUD. Bearing in mind that this tetrahedron is just the upper part of what is assumed as being part of a larger tetrahedron and not showing, it is assumed for purpose of S illustration that a point has been selected within this larger tetrahedron to indicate a specific mixture composed of 4 components. For convenience, the point is taken as A. If from A perpendiculars are erected to each of the four planes then there are designated at least three of them by lines which are shown and indicated as follows: AB', A'C', A'D. The fourth perpendicular goes from A to the point in the plane beneath which is the assumed base of the original larger regular tetrahedron. Since thelarger tetrahedron is not shown for the reason that it would only add confusion, this perpendicular is indicated simply by the line AA'A'.

What has been said previously is illustrated in a slightly different aspect actually showing both the large tetrahedron and the plane in Figure 2. In this instance again the regular tetrahedron must be presented in a somewhat distorted aspect in order to show what is desired. The present invention is concerned with a cogeneric mixture derived from 4 components, to wit, ethylene oxide, propylene oxide, glycide, and hydrophobic reactant which is susceptible to reaction with the 3 enumerated alkylene oxides. These 4 components or initial reactants represent the 4 points or apexes of the regular tetrahedron and it will be noted that in this presentation the l apexes are marked A, C and D. A represents 100% of propylene oxide, B represents 100 of ethylene oxide, D represents 100% of glycide and C represents 100% of hydrophobic reactant.

Referring momentarily to what has been said in regard to Figure 1 it will be noted that a perpendicular which is comparable is shown a a line connecting point A with point AA. More important, however, is this fact, that when a plane is placed parallel to the base such plane or" necessity has the same configuration as the base. If one selected some particular figure in the base, for instance a triangle, a square, a rectangle, a pentagon, or the like, and drew lines from the corners or apexes of such plane figure in the base, to the top apex D, then that same figure but in a reduced size would appear in the intersecting plane TUV shown in this particular il'gure. TUV is the equilateral triangle furnished by the intersecting plane VTXYZ which intersects the regular tetrahedron parallel to the base.

It is convenient to ignore temporarily Figure 8 and pass to Figure 4. Figure 4 again depicts the regular tetrahedron but actually is somewhat distorted, of course. It also shows a space or block within the tetrahedron and since the block is assumed to be somewhat above the base, each and every point in this block represents a 4-component system. The present invention is concerned with those compositions which are characterized and specified by this particular block. As stated previously ii S-dimensional models could be employed all that would be necessary would be to prepare the tetrahedron from sheets of plastic so that 100 sheets, for example, would represent the distance between the base and the apex, cut out the space represented by the block, and fill it in with colored wax or another plastic, thus the representation would be complete. This is not possible due to limitations which have been pointed out previously.

The composition represented by the block which is really a truncated trapezoidal pyramid is designated by E, F, G, H, I, J, K, and L. Bear in mind that, as has been stated, the base of the truncated pyramid, that E, F, G, and H, does not rest on the bottom of the equilateral base triangle. As has been pointed out previously, point D represents glycide. The base triangle represents the three other components and obviously 0% glycide. For purpose of what is said herein, the lower base of the truncated pyramid E, F, G, H, is a base parallel to the equilateral triangle but two units up, i. e., representing 2% of glycide. Similarly, the upper base of the truncated pyramid I, J, K, L lies in a plane which,is 25 units up from the base, to Wit, represents 25 glycide. Specifically, then, this invention is concerned with the use of components in which the glycide component varies from 2% to 25% glycide. The problem then presented is the determination of the other three components, to wit, ethylene oxide, propylene oxide, and the hydrophobic reactant.

A simplification of the problem of characterizing a 4-component system which enters into the spirit of the present invention is this: If the amount of one component is determined or if a range is set, for example, 2% to 25% of glycide, then the difference between this amount and 100%, i. e., 75% to 98%, represents the amounts of percentages of the other three components combined, and these three components recalculated to 100% bases can be determined by use of an ordinary triangular graph, such as employed in our previously mentioned eight copending applications, Serial Nos. 109,791 to 109,797, inclusive, and Serial No. 110,332.

This becomes even simpler by reference to Figure 1 in which itwill be assumed that the amount of glycide is v ithin the range of 2% to 25%, and since the base of the tetrahedron is an equilateral triangle the plane parallel to the base and through any point on the perpendicular which represents 2% to 25%, must also be an equilateral triangle.

In Figure 1 from the point A there are the three conventional perpendiculars to the sides as employed in a l-cornponent system, i. e., A'B, AC, AB'; however, by definition the lines A'B, A'C, and AD' must be perpendicular to the faces. This means that the angles G'D'A, A'CF', and ABE, are right angles. Similarly, the angles D'G'A', A'EB', and A'F'C represent the angles between the faces of a regular tetrahedron and thus are constant. Since two angles of the triangle are the same, the third angle must be the same and it means that these three triangles are similar. This means that the ratio between the perpendiculars to the sides, that is, A'B, AC, and AD bear the same ratio to each other as the perpendiculars to the edges bear to each other to wit, AE", AF', and AG'. Therefore, when the fourth component, for example, glycide, has been set within the range 2 to 25%, the remaining three components consisting of 75% to 98% recalculated back to 100% bases, can be calculated or represented by the same triangular graph as is conventional and as employed in the abovementioned co-pending applications, Serial Nos. 109,'791 through 109,797, filed August 11, 1949, and Serial No. 110,332.

Actually, as far as the limiting points in the truncated pyramid are concerned, which has been previously referred to in Figure 4, it will be noted that in the subsequent text there is a complete table giving the composition of these points for each successive range of glycide. In other words, a perfectly satisfactory repetition is available by means of these tables from a practical standpoint without necessarily resorting to the data of Figure 3.

Figure 3 shows a triangle and the three components other than glycide. These three components added together are less than 100%, to wit, 75% to 90%, but for reasons explained are calculated back to 100%. This point is clarified subsequently by examination of the tables. It will be noted also that in Figure 3 there is shown not only a trapezoid indicated by points 8, 9, l and H which represent the bases (top, bottom, or for that matter, intermediate) of the truncated pyramid, but also area in which the com position is of particular effectiveness as a demulsifier. The circular and triangular areas can be ignorecLif desired as far as the general aspect of the present invention goes, but since we are making direct comparison with our aforementioned copending applications, to wit, Serial Nos. 109,791 to 109,797, inclusive, and Serial No. 110,332, we are employing exactly the same identical figure for ease of comparison.

Previous reference has been made to our 00- pending applications, Serial Nos. 109,791 to 109,797, inclusive, all filed August 11, 1949, and Serial No. 110,332, filed August 15, 1949. As stated, these were concerned with products or co-generic mixtures obtained from three'components-an oxyalkylation-susceptible hydrophobic reactant, ethylene oxide and propylene oxide. The present invention contains the fourth component, glycide. At first glance it may seem rather odd that the introduction of glycide in even relatively small amounts radically affects the nature of the resultant products.

Comparing ethylene oxide, propylene oxide, and glycide, it is to be noted that in ethylene oxide the ratio of carbon atoms to oxygen is 2 to l, in propylene oxide 3 to 1, and in glycide 1.5 to 1. This carbon-oxygen ratio, of course, explains the greater solidifying efiect of glycide in comparison with either ethylene oxide or propylene oxide but the principal difference is that in using glycide one can obtain a variety of branched chain or forked structures.

Assume that the hydrophobic oxyalkylationsusceptible reactant has one or more terminal groups which may be indicated thus:

R simply represents a divalent radical. Reaction with ethylene oxide, propylene oxide and glycide may be shown thus:

-RO*(J2H|OH P.O-C3H5OH on -u-o-c,n,on

If one employs ethylene oxide first and then glycide, or propylene oxide first and then glycide, one obtains an increased hydrophile effect at the terminal groups for the reason there are two hydroxyls present instead of one, which additionally are susceptible to more complex micellar formation by virtue of association involving two hydroxyls. This is illustrated in the following manner:

It becomes obvious that glycide can be em ployed in a number of ways, three of which are as follows: (a) immediately and preceding the introduction of either ethylene oxide or propylene oxide; (17) after ethylene oxide has been introduced and before propylene oxide has been introduced, or vice versa; after propylene oxide has been introduced and before ethylene oxide has been introduced; and finally (c) glycide can be introduced in a terminal position after both ethylene oxide and propylene oxide have been introduced. Needless to say, lycide could be introduced in all three of these positions, or in two of the three. For that matter some ethylene oxide can be introduced, then glycide, and more ethylene oxide, or some propylene oxide, then glycide and more propylene oxide.

Suggestive of such variations are the following formulas:

For sake of simplicity it appears advisable to present mixtures obtained from three components first (the oxyalkylation-susceptible hydrophobic reactant, ethylene oxide and propylene oxide) and then carry the three-component system into the four-component system by after-treatment with glycide within the stipulated proportions. After such description it becomes obvious that other modifications of the kind previously suggested readily present themselves and need only minor description. For this reason the subject matter immediately following is in substantially verbatim form as it appears in our co-pending applications, Serial Nos. 109,791, 109,792, and 109,793, all filed August 11, 1949, and Serial No. 110,332, filed August 15, 1949.

PART 2 As has been pointed out previously, for simplicity of presentation and particularly for convenience of comparison with certain co-pending applications, particularly Serial Nos. 109,791, 109,792 and 109,793, all filed August 11, 1949, and Serial No. 110,332, filed August 15, 1949, the text immediately following is concerned with the derivatives obtained without the use of glycide. The conversion or modification of the three-component system to a four-component system is presented in Part 4.

Reference is made to the accompanying Figure 3, in which there is presented a triangular graph showing the composition of certain glycol ethers of alpha-terpineol, or cogeneric mixtures thereof, derivable from alpha-terpineol and ethylene oxide alone, or alpha-terpineol and propylene oxide alone, or alpha-'terpineol, and both propylene oxide and ethylene oxide, in terms of the initial reactants. We have found that effective demulsifying agents lie approximately within a small and hitherto unsuspected area indicated by the trapezoid determined by the points 8, 9, l and II. More specifically, particularly effective demulsifying agents appear within a smaller range, as set forth approximately by the area indicated by the segment of a circle in which the area of the segment is limited to derivatives in which alpha-terpineol contributes at least 4% by weight of the ultimate compound or cogeneric mixture.

The circle itself is identified by the fact that the points 1, 3 and 6 appear on the circle. The more effective of these better compounds or oogeneric mixtures are those which appear within the triangle which represents part of the circle and part of the segment, to wit, the triangle identified by the points I, 3 and 6. The most effective compounds or cogeneric mixtures of all are those which fall within the inner central triangle of the larger outer triangle identified by the points I, 3 and 6, to Wit, the smaller triangle identified by the points 2, 4 and 5. The most outstanding of these effective compounds or cogeneric mixtures is one which appears to fall substantially at the center of the smaller triangle, identified by point 1. This particular point is obtained by treating one mole of alphaterpineol with moles of propylene oxide, followed by treatment with 18 moles of ethylene oxide.

In spite of the unique character of the compounds or cogeneric mixtures previously described, we have made additionally an invention within an invention. This can be illustrated by reference to the compounds or cogeneric mixtures whose composition is determined by the inner triangle, 2, 4, 5. This preferred class of derivatives, or for that matter, all the herein described products, can be made in three different ways: (a) by adding propylene oxide first and then ethylene oxide; (b) by adding ethylene oxide first and then propylene oxide; or (c) by adding the two oxides by random, indifferent, or uncontrolled addition so as to produce a polyglycoletlier in which the propylene radicals and ethylene radicals do not appear in continuous succession but are heterogeneously distributed.

We have found that if propylene oxide is added first, and then ethylene oxide is added, the compounds or cogeneric mixtures so obtained are invariably and inevitably more effective as demulsifiers, and are also more eifective for other purposes than the comparable glycol ethers of alphaterpineol made by combining the three reactants in any other sequence. This will be explained further with additional illustrations subsequently.

As an illustration of the preparation of various compounds or cogeneric mixtures, and particularl the most desirable ones, and also those which are helpful in setting the limits in the graph previously referred to, the following examples are included. In connection with these examples it will be noted that the oxyalkylation of alphaterpineol, i. e., by treatment with ethylene oxide or propylene oxide or a mixture of the two, is conventional. The procedure is conducted in the same manner employed in connection with other alcohols Or the like, and generally an alkaline catalyst is employed. See, for example, U. S. Patent No. 2,440,093, dated April 20, 1948, to

7 i9 Israel, and British Patent No. 602,591, applied for February 12, 1945.

Example 1a The reaction vessel employed was a stainless steel autoclave with the usual devices for heating, heat control, stirrer, inlet, outlet, etc, which is conventional in this type of apparatus. The capacity was approximately 40 gallons. The stirrer operated at a speed of approximately 250 R. P. M. There were charged into the autoclave 15.4 pounds of alpha-terpineol There were then added 12 /2 ounces (approximately 5% by weight) of ground caustic soda. The autoclave was sealed, swept with nitrogen gas, and stirring started immediately and heat applied, and the temperature allowed to rise to approximately 150 C. At this point addition of propylene oxide was started. It was added continuously at such speed that it was absorbed by the reaction as rapidly as added. The amount of propylene oxide added was 88 pounds. The time required to add this propylene oxide was slightly in excess of one hour, about 1 A1 hours. Durin this time the temperature was maintained at 150 to 160 C., using cooling water through the inner coils when necessary and otherwise applying heat if required. At the end of the addition of the propylene oxide there was added ethylene oxide, as previously indicated.

- The amount of ethylene oxide added was 80 pounds. The temperature employed, and operatin conditions, were the same as with the addition of propylene oxide. It is to be noted, however, that ethylene oxide appears to be more reactive and the reaction seems to require a greater amount of cooling water to hold the temperature range indicated. The time required to add the ethylene oxide was about the same, or slightly less, usually just a little more than an hour.

During the addition of the propylene plus ethylene oxides, the pressure was held at approximately pounds per square inch gauge pressure, or less. When all the oxide had been added (ethylene oxide being the final addition in this particular instance) the autoclave was permitted to stay at the same temperature range for another half hour, even longer if required, or until the gauge pressure had been reduced to zero or substantially zero, indicating the reaction was complete. The final product was an oily material,

somewhat viscous in nature, resembling castor oil and having a definite alpha-terpineol or terpene-like odor. It was soluble in water and also soluble in non-aqueous solvents, such as aromatic hydrocarbons, and others, although not soluble in some non-polar hydrocarbon solvents. The final yield was substantially the total weight of the initial reactants.

Example 2a The same procedure was followed as in Example la, except that a mixture, to wit, 168

pounds of propylene oxide and ethylene oxide,

were added over a two-hour period. This mixture of ethylene oxide and propylene oxide was obtained from 88 pounds of propylene oxide and pounds of ethylene oxide. In this instance again the time range, temperature, and pressure were kept substantially the same as in Example la,

preceding.

Example 4a different ways:

(a) first adding the propylene oxide and then the ethylene oxide; (12) first addpropylene ox1de together and adding them simul- The same procedure as in Example 1a, pretaneously. ceding, was conducted on a laboratory scale em- The data are summarized in the following ploymg a small autoclave having a capacity of aptable:

Alpha-'lerpineol Propylene O xidc Ethylene Oxide Point on graph F. N Weight Weight Weight identifying Weight M l 1 PerCent, Weight M ml Per Cent, Weight Molql Per Cent, specific Used, in in Final Used, in i .in Final Used, in y-" in Final Glycol Grains Glycol GlLKIlS O Glycol Grams Glycol Ether Ethei Ether Ether .4. 154 1. 0 15.0 462 7. 95 45 411 9. 54 1 154 1.0 10. 0 771 1a. 3 50 515 14. 0 40 2 154 1. 0 5.0 1, 700 20. 55 1, 232 as. o 40 3 154 1. 0' 15. 0 593 11. 95 592 15. 77 45 4 154 1. 0 5. o 1.542 25. 5 5o 1, 290 21. o 45 5 154 1. 0 5. 0 1, 390 23. 95 45 1. 5-12 $5.10 5 154 1. o s. 45 866 14. 95 47. 800 15. 17 44 7 154 1.0 9.2 812 14.0 48.6 704 15.0 42.2 154 1. 0 9. 0 s12 14. 0 47. 4 745 17.0 4-5. 5 154 1. o s. 5 s12 14. 0 45. 2 792 is. o 45. c 154 1. 0 8.7 570 15. 0 49. 0 748 17.0 -12. 3 154 1. 0 5. 45 555 14. 95 47.55 500 15.17 44 7 154 1. o s. 3 870 15. 0 45. 7 s25 10. o 45. n 154 1. 0 s. 2 .2: 4 15. 0 49. 5 792 18. n 42. 3 154 1. n s. o 934 15. 0 4s. 5 s55 19. 0 43. 5 154 1.0 7. s 934 15. o 47. 4 s50 20. 0 44. s 154 1. 0 2 0 200 a. 45 25 415 9. 45 54 3 s 154 1. 0 4. 0 1, 000 17. 25 25 2, 590 51. 2 7o 11 9 154 1. 0 4. 0 2, 025 50. 4 770 17. 5 20 1 111 154 1.0 20. 0 45 7. 95 50 154 s. 5 20 a 11 1 Within inner triangular area. 1 Duplicated for convenience. 3 Indicates limits of trapezoidal area.

ene oxide employed was 240 grams.

same as on a larger scale.

place in the laboratory autoclave in a fraction the time required in the larger autoclave; in fact,

in many instances, absorption was complete 5 to 10 or 15 minutes, as compared to one-hour Needless to say, on a large scale, addition must be conducted carefully because there is an obvious hazard in handling a large quantity of material in an autoclave which is not necessaril present in the use of a small on a larger scale.

vessel.

Example 5a The same procedure was followed as in Example 4a, preceding, in every respect, except the variation described in Example 241, preceding, 1. e., the ethylene oxide, was added first and the propylene oxide added last.

Example 6a The same procedure was followed as in Example 4.a in every instance, except the modification previously described in Example 3a, to Wit. the propylene oxide and the ethylene oxide were mixed together and added in approximately minutes to one-half hour. the procedure was identical with that described Example 4a.

The following table includes a series of compounds or cogeneric mixtures which have been selected as exemplifying the herein included prod- Types of the herein noted compounds or cogeneric mixtures have been produced in three ucts.

In all other respects touching homologues.

In the preparation of the above compounds the alkaline catalyst used was either flake caustic soda finely ground with mortar and pestle, or powdered sodium methylate, equivalent to 5% by weight of the alpha-terpineol which was employed.

For reasons which are pointed out hereinafter in greater detail, it is substantially impossible to use conventional methods and obtain a single glycol ether of the kind described. Actually, one obtains a cogeneric mixture of closely related or These materials invariably have high molecular weights and cannot be separated from one another by any known method without decomposition. such a mixture represent the contribution of the various individual members of the mixture.

Although one cannot draw a single formula and say that by following such and such pro cedure one can obtain or or of The properties of such single compound, yet one can readily draw conventionally.

the formulas of a large number of compounds which appear in some of the mixtures described elsewhere, or can be prepared readily as components of mixtures which are manufactured Such formulas, representing significant portions of various mixtures, are of distinct value insofar that they themselves characterize the invention, i; e., describe individual components which are typical of the members of the cogeneric mixture. mulas, since ROH can represent alpha-terpineol, R0 is the ether radical obtained from alpha-terpineol by removal of the hydrogen atom attached to the oxygen atom.

In the following for- If one selects any hydroxylated compound and subjects such compound to oxyalkylation, such as oxyethylation, or oxypropylation, it becomes obvious that one is really producing a polymer of the alkylene oxide except for the terminal group. This is particularly true where the amount of oxide added is comparatively large, for instance, 10, 20, 30, 40, or 50 units. If such a compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent, which, for the sake of convenience, may be indicated as RO(C2H4O)30H. Instead, one obtains a cogeneric mixture of closely related homologues, in which the formula may be shown as the following: RO(C2H4O)11H, wherein n, as far as the statistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25, and perhaps less, to a point where it may represent 35 or more. Such mixture is, as stated, a cogeneric, closely related series of touching homologous compounds. Considerable investigation has been made in regard to the distribution for linear polymers. Attention is directed to the article entitled Fundamental principles of condensation polymerization, by Paul J. Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either experimental or mathematical examination, of indicating the exact proportion of the various members of touching homologous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i. e., the ability to describe how to make the product under consideration and how to repeat such production time after time with out difiiculty, it is necessary to resort to some other method of description.

Actually, from a practical standpoint, it is much more satisfactory, perhaps, to describe the ultimate composition in terms of the reactants, i.e., alpha-terpineol and the two alkylene oxides. The reason for this statement is the following: If one selects a specific compound, it must be borne in mind that such compound is specific only insofar that the cogeneric mixture in terms of a statistical average will conform to this formula. This may be illustrated by an example such as RO(C3H60)15(C2H40)18II. If one combines the reactants in the predetermined weight ratio so as to give theoretically this specific component, and assumingly only one chemical compound were formed, what happens is that, although this particular compound may be present in a significant amount and probably less than 50%, actually one obtains a cogeneric mixture of touching homologues in which the statistical average does correspond to this formula. For instance, selecting reactants, which, at least theoretically, could give the single compound what actually happens is that one obtains a sort of double cogeneric mixture, for the reason that in each batch or continuous addition of an alkylene oxide a cogeneric mixture is formed. Since the present products require the addition of at least two diiferent multi-molar proportions of each of two different alkylene oxides (ethylene oxide and propylene oxide) it becomes obvious that a rather complex cogeneric mixture must result.

This can be best illustrated by example. Assume that one is going to use the indicated ratio, to wit, one pound mole of alphaterpineol, 15 pound moles of propylene oxide, and 18 pound moles of ethylene oxide. The initial step involves the treatment of one pound mole of alphaterpineol with 15 pound moles of propylene oxide so as to yield theoretically RO(C3H60)15H; actually, as pointed out, one does not obtain RO(C3H6O)1LH in which n is 15, but really one obtains a cogeneric mixture in which there are present significant amounts of homologues in g which n varies from 16, 11 and 12 on up to 17, 18 and possibly 19 or 20. A statistical average, however, must, of course, correspond to the proportion of the initial reactants, i. e., a compound of the formula RO(C3H60)15H which is present undoubtedly to a significant extent.

When this cogeneric mixture is then subjected to reaction with 18 moles of ethylene oxide, it becomes obvious that, although one may obtain some RO(C3Hr,O)1s(CzI-I4O)18Ii, yet this particular product can only be present to a minor extent for reasons which have been described in conection with oxyethylation and which now are magnified to a greater degree by oxypropylation, Stated another Way, it is probable that the cogeneric mixture represents something like RO"(C3HGO)1L(C2H40)7UH in which, as previously pointed out, components present in important percentages are those in which 11 could vary from anywhere beginning with 1D to 12, on up to 18 or 20. By the same token, components present in important percentages are those in which 11 could vary anywhere from 13 or 14 up to the lower 20s, such as 21, 22, 23 or 24. Indeed, homologues of a lower or a higher value of n and n will be present in minor amounts, the percentage of such components decreasing, the further removed they are from the average composition. However, in spite of such variation in regard to the cogeneric mixtures, the ultimate composition. based on the ingredients which enter into it and based on the statistical average of such constituents, can still be expressed by the formula RO(C3HeO-),15(C2H4O)13H. This actual product exists to some degree in the cogeneric mixture, but it should be looked upon as statis- 16 tical average formula rather than the structure of a single or predominant compound in the mixture.

A second reason for employing a reaction mixture to describe the product is the fact that the molal proportions need not represent whole numbers. We have just pointed out that if one selects molal proportions corresponding to RO(C3H60)15(C2H40)13H, then the constituents are added in actual molar proportions based on Whole numbers. If, however, one selects a point in the inner triangular area, which, when recalculated in terms of molar proportions, produces a fractional number, there is still no reason why such proportions of initial reactant should not be adopted. For instance, one might select a point in the triangular graph, which, when cal culated in terms of molecular proportions, represents a formula, such as the following:

This, of course, would be immaterial, for the reason that if one starts with a pound mole of alphaterpineol and adds 15.5 pound moles of propylene oxide, one will obtain, on the average, a mixture closely comparable to the one previously described, using exactly pound moles of propylene oxide instead of 15.5. Such mixture corresponds to the compound RO(C3HsO)15.5H only in the sense of the average statistical value, but not in the sense that there actually can be a compound corresponding to such formula. Further discussion of this factor appears'unnecessary, in light of what has been said previously.

Such mixture could, of course, be treated with 18 pound moles of ethylene oxide. Actually, all that has been said sums up to this, and that is that the most satisfactory way, as has been said before, of indicating actual materials obtained by the usual and conventional oxyalkylation process is in terms of the initial reactants, and it angular graph, from a practical aspect, invari ably and inevitably represents the statistical average of several or possibly a dozen or more closely related cogeners of almost the same composition, but representing a series of touching homologues. The particular point selected represents at least the composition, of the mixture expressed empirically in the terms of a compound representing the statistical average.

Previous reference has been made to the fact that comparatively few oxyalkylated derivatives of simple hydroxylated compounds find utility in actual demulsification practice. We have pointed out that we have found a very few exceptions to this rule. .ihe fact that exceptions exist, as in the instant invention, is still exceedingly difficult to explain, if one examines the slight contribution that the end group, derived from the hydroxylated material, makes to the entire compound. Referring for the moment to a product of the kind which has been described and identified by the formula RO(C3H60)15(C2H40)18H, it becomes apparent that the molecular weight is in the neighborhood of 1800 and actually the alpha-terpineol contributes less than 10% of the molecular weight. As a matter of fact, in other comparable compounds the alpha-terpineol may contribute as little as 4% or 5% and yet these particular compounds are effective dernulsifiers. Under such circumstances, it would seem reasonable to expect that some other, or almost any other, cyclic S-carbon atom compound comparable to alpha-terpineol would yield derivatives .is obvious that any particular point on the triequally effective. Actually, this is not the case. We know of no theory or explanation to suggest this highly specific nature or action of the compound or cogeneric mixture derived from alphaterpineol.

Referring to an examination of the previous list of 32 compounds, it is to be noted that in certain examples, for instance, formulas 9 to 15, inclusive, all the propylene oxide is added first and then the ethylene oxide is added. Compounds indicated by Examples la to 8a are substantially the same, as far as composition goes, but are reversed, insofar that the ethylene oxide is added first and then the propylene oxide.

Other compounds having substantially the same ultimate composition, or at least, very closely related ultimate compositions, having a further variation in the distribution of the propylene oxide and ethylene oxide, are exemplified by Formulae 16 to 32, inclusive.

As has been pointed out previously, for some reason which we do not understand and for which we have not been able to offer any satisfactory theory, we have found that the best compounds, or, more properly, cogeneric mixtures, are obtained when all the propylene oxide is added first and then all the ethylene oxide is added. Although this is true to at least some extent in re to all compositions within the trapezoidal area in the triangular graph, yet it is particularly true if the composition comes within the segment of the circle previously referred to in the drawing. In such event, one obtains a much more effective demulsifier than by any other combina tion employing ethylene oxide alone, propylene oxide alone, or any variation in the mixture of the two, as illustrated by other formulas. In fact, the compound or cogeneric mixture so obtained, as far as demulsification is concerned, is not infrequently at least one-third better than any other derivative obtained in the manner described involving any of the other above varia tions.

The significance of what has been said previously becomes more emphatic when one realizes that, in essence, we have found that one isomer is a more effective demulsifying agent than another isomer. The word isomer is not exactly right, although it is descriptive for the pur pose intended insofar that we are not concerned with a single compound, but with a cogeneric mixture, which, in its statistical average, corresponds to such compound. Stated another way, if we start with one pound mole of alpha-terpineol, 15 pound moles of propylene oxide and 18 pound moles of ethylene oxide, we can prepare two different cogeneric mixtures, which, on a statistical average, correspond to the following:

and RO C3H6O)15(C2H4O)18H. There is nothing we know which would suggest that the latter be a much more effective demulsifying agent than the former and also that it be more effective for other industrial purposes. The applicants have had wide experience with a wide variety of surface-active agents, but they are unaware of any other similar situation, with the exception of a few instances which are the subject-matter of other co-pendin applications, or under investigation. This feature represents the invention with an invention previously referred to, and thus, becomes the specific subject rnatter claimed in our co-pending applications Serial Nos. 110,332,

smas es filed :August Lid/11949, :a-nd 1109;793, rfiled August 11, 19.49.

Reference 'has'been'zmade :to :the fact that the 'productherein specified, and'particularlyior use as .a demulsifienirepresents a cogenericimixtureof closely related hOmOIOgueS. .This does notzmean that ones-could not use combinations :ofrsuchco- .generic :mixtures. .For :instance, .in the .previous table .data have been: given.forzpreparation'otcogeneric .mixtures :which statistically correspond, respectively,dto points [,3 andzfi. lsuch three-tcogeneric mixtures rcould be :combined ;in equal weightsso. asztoigivesacombinationin' which the mixed statisticaliaverage would correspond closely to point I.

Similarly, one could clothe-same thing by preparing cogeneric mixtures corresponding :to points "2, i4 and-"5, described in .the previous table. Such mixture could ithenbe combined in equal parts :by weight to give another combination which would closely correspond (in a mixed statis ticalbasistopointl. Nothing said'here'in'is intended'to' preclude such combinations of this or similar type.

' Throughout this specification reference has been made to alphaterpineol. We have employed a commercial product sold by the Hercules Powder Company under the designation Terpine'ol3l8 which consists of"85% alpha-terpineol and 'beta terpineol. This mixture melts sufficiently low for the product to be a liquid at ordinarytemperatures, whereas, alphaterpineol is a mushy .crystallinepr'oduct, which is somewhat more difiicult to handle. 7 'Terp'ineol 318 is also approximately one cent a pound cheaper than alpha-terpineol. It is understood that-Wherever we have specified alphaterpineol, this particular product can be employed. This, of course, is obvious, for thereason that, if desired, one can mix alpha terp'ineol withsome other product susceptible-to oxyethyla tion and oxypropylation, such as menthylcyclohexanol, and subject the two products to simultaneous 'oxyalk'ylation'. v "Foria number of reasons, it is ordinarily desirable .to use ajproce'durein which only'one aroductis reacted ata time.

At times wehave examined samples of'lIerpineol 318 which appeared acidic, 'due to the presence apparently .o'f *aresinic acid. Attempt to .oxyalkylate causes difficulty because the alkaline "catalystisneutralized. "In such cases 'the acidity should be neutralized and then the customary amount of "catalyst added.

'Itis possible that the oxyalkylation, particularly ox propylation, -of'Terpineol318 is a 'bit slower than *thatiof straight alpha-iterpineol, due to'the pre'sence'oibeta-fterpine'ol.

PART :3

.As has .been pointed out previously, one way of preparing compounds .or cogeneric -mixtures to'be used in the present invention is to prepare a-series .of compounds .identified .as :Examples A through-S, in.l?art.2, preceding, or Examples :1a through .611, as described inPart-2, preceding.

TReferring .nowlto Figure 4, itisobvious that :the threecomponents (ignoring iglycide) are represented .by .either the .lower trapezoidal base .in Figure 4, i. e., "E, .F, IG,.H, .or -I, JFK, L and then recalculated 'to..100% basis as a .tertiary mixture; such three. components .must'lie withinthe trapezoid 8, 9, l0, LI in Figure 3,.and the preferred proportions: are within the .arc of the .circlepreviously described. in Part v2 and .shownin Eigure 3, ,or .more .specifically withinthe l large triangle 18 1,3,:6 orithe'.smallertrianglel, A, 5, orzevenzmore specifically atapproximatelypoint 1. :Statedanother :way, if .one selects the proportion .of the three components or. reactans ignoringglycide) and at any stage employs .sufiicient ,glycidezso that on .the basis .of the" quaternary mixture such glycide represents ;2,% .to of the .total :by weight, vthen :and .in that event .one has .automatically obtained a .oomposition that is within the limits .of .the truncated trapezoidal pyramid identified byE, .F,'G, H-I, .J,.K, Lin.:Figure-f4. This. represents :the cogenericmixture or reaction product :in :terms of initial reactants with the proviso :that the .glycide icontent .is .-2% to 251% by :vveight and .that theremaining three components recalculated to 100% basis (leaving out glycide for-the moment) came within the trapezoidal area:indicated-.by:58,:9,sill,lzlgon theztriangulargraphto'wit, Figure 3.

We have prepared- .derivatives of the kind -.herein described :in 'a scale vvarying i from 'a few thundred .grams or less, .in the laboratory .to .hundreds :of pounds onqaplantrscalev vInzpreparing a large number of examples we have found it particularly advantageous to use laboratory equipment which :permits icontinuous-oxypropylationand oxyethylation. More specific reference will be .made .to treatment with glycide, subsequently in the text. The :oxyethylation-step is, of :course, the .same "as zthe aoxypropylation step insofar that two low "boiling ;liquids are handled in each instance. Whatimmediately tfollows refers to .oxypropylationrand .it .is iunderstood that oxyethylation .can be :handled nonveniently ;in exactly the same Way.

The ioxypropylation procedure.employedinathe preparation.ofiderivativesjfrom.polyhydricreactants .has :been :uniformly :the .asame, particularly inlight ot Lthefact that .a continuous loperating procedurelwaszemployed. iIn.thistpartioular, pro-- cedure the autoclave was .a rconventional autoclave, ,made ofistainless steel and having arcapacity..of approximately gonegallon, :andza iWOIlking pressure of 1,000 poundszgaugejpressure. The autoclave was equipped with the iconventional devices andi'openings, such astthe variablestirrer operating at speeds :from .50 R. P. M. 1120 .500 R. P. M., thermometer wellaand thermocouplerfor mechanical thermometer; 1 emptying outlethpressure gauge, ,manual vent .line; charge -hole .afiorv initial. reactants; ajattleastone connection'ior conducting the incoming alkylene .oxide, .such as propylene oxide, to the bottom .of the autoclave; along with suitable'devicesfor .both coolingand heating the autoclave, suchias a cooling jacket and, preferably, coils -.in addition thereto, with thejacket so arranged that it.is suitable forheating withsteam or cooli g With water, ;and. fur;- ther equipped .with electrical heating adevices. Such autoclavesare, of course, in essence small scale replicas of :the usual conventionalautoclave used in oxyalk-ylation procedures. 7

Continuous operation, or .-substantially continuous operation, is achieved by the use of aseparate container to hold-the alkylenewxide being employed, particularly propylene oxide. .The container consists essentially of .a laboratory bomb having .acapacity of about one-half .galion, or somewhat in excess 'thereof. This bomb was equipped, also, :with :an .inlet for charging, andan outlet tube going -.to the bottom of the container sofas to .permit .dischargingof 'alkylene oxidein-the liguidphaseto theautoclave. Other conventional vequipment.consists,.o f .coursecof the rupture disc, .pressure gauge, :sight feed iglass,

thermometer connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use and the connections between the'bomb and the autoclave were flexible stainless hose or tubing so that continuous weighings could be made without breaking or making any connections. This also applied to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass, protective screens, etc.

With this particular arrangement practically all oxypropylations become uniform in that the reation temperature could be held within a few degrees of any point selected in this particular range; for instance, in most cases we have selected a point of approximately 160 C. to 165C as being particularly desirable and stayed within the range of 155 to 180 C. almost invariably. The propylene oxide was forced in by means of nitrogen pressure as rapidly as it was absorbed, as indicated by the pressure gauge in the autoclave. In case the reaction slowed up so the temperature dropped much below the selected point of reaction, for instance, 160 C., then all that was required was that either cooling water was cut down or steam was employed, or the addition of propylene oxide speeded up, or electric heat used in addition to the steam in order that the re action procedures at or near the selected temperatures be maintained.

Inversely, if the reaction proceeded too fast the amount of reactant being added, 1. e., propylene oxide, was cut down or electrical heat was cut off, or steam was reduced, or if need be, cooling water was run through both the jacket and the cooling coil. All these operations, of course, are dependent on the required number of conventional gauges, check valves, etc., and the entire equipment, as has been pointed out, is conventional and, as far as I am aware, can be furnished by at least two firms who specialize in the manufacture of this kind of equipment.

Attention is directed to the fact that the use of glycide requires extreme caution. This is particularly true on any scale other than small laboratory or semi-pilot plant operations. Purely from the standpoint of safety in the handling of glycide, attention is directed to the following: (a) If prepared from glycerol monochlorohydrin, this product should be comparatively pure; (b) the glycide itself should be as pure as possible as the effect of impurities are difiicult to evaluate; (c) the glycide should be introduced carefully and precaution should be taken that it reacts as promptly as introduced, i. e., that no excess of glycide is allowed to accumulate; (d) all necessary precaution should be taken that glycide cannot polymerize per se; (e) due to the high boiling point ofglycide one can readily employ a typical separatable glass resin pot as described in the co-pending application of Melvin De Groote and Bernhard Keiser, Serial No. 82,704, filed March 21, 1949 (now Patent No. 2,499,370, dated March 7, 1950), and offered for sale by numerous laboratory supply houses. If such arrangement is used to prepare laboratory scale duplications, then care should be taken that the heating mantle can be removed rapidly so as to allow for cooling; or better still, through an added opening at the top the glass resin pot or comparable vessel should be equipped with a stainless steel cooling coil so that the pot can be cooled more rapidly than mere removal of mantle. If a stainless steel coil is-introduced it means that conventional stirrer of the paddle type is changed into the centrifugal type which causes the fluid or reactants to mix due to swirling action in the center of the pot. Still better, is the use of a laboratory autoclave of the kind previously described in this part; but in any event, when the initial amount of glycide is added to a suitable reactant, such as sorbitol, the speed of reaction should be controlled by the usual factors, such as (a) the addition of glycide; (b) the elimination of external heat, and. (c) use of cooling coil so there is no undue rise in temperature. All the foregoing is merely conventional but is included due to the hazard in handling glycide.

Example 11) It is to be noted that the procedure followed can be conducted on any convenient scale, that is, on eithera small laboratory sca1e',"semi-plant scale, pilot plant scale, or large plant scale. We have conducted experiments employing equipment of all such various sizes. Our preference even on a laboratory scale is to use continuous introduction of ethylene and propylene oxide, although this is not necessary. The introduction may be batchwise. Previous reference has been made to the catalyst used in connection with ethylene oxide and propylene oxide. These same alkaline catalysts, particularly caustic soda, caustic potash, sodium methylate, etc., are equally satisfactory with glycide which in many ways seems to be at least as reactive as ethylene oxide and possibly more reactive than propylene oxide.

The reaction vessel employed was a stainless steel autoclave with the usual devices for heating, heat control, stirrer, inlet, outlet, etc., which is conventional in this type of apparatus. The capacity was approximately 40 gallons. The stirrer operated at a speed of approximately 250 R. P. M.

The particular piece of equipment employed was adapted for the use of glycide without pressure, as well as the useof ethylene oxide and propylene oxide with pressure. Stated another way, instead of serving as an'" autoclave only it was also equipped with a water-cooled condenser which could be shut off when used as an autoclave. It was equipped also with an equivalent of a sepa-. ratory' funnel and an equalizing pressure tube so that a liquid such as glycide could be fed continuously at a dropwise or faster rate into the vessel and the rate controlled by visual examination. For convenience, this piece of equipment will be referred to as an autoclave.

There were charged into the autoclave 15.4 pounds of alpha-terpineol. There were then added 12.5 ounces (approximately 5% by weight)" of ground caustic soda. After being charged the autoclave was sealed, swept with nitrogen gas, and stirring started immediately and heat applied, and the temperature allowed to rise to approximately C.

The glycide employed was comparatively pure. 7.5 pounds of glycide were used. This was charged into the upper reservoir vessel which had been previously flushed out with nitrogen and was the equivalent of a separatory funnel. The glycide was started slowly into the reaction mass in a dropwise stream. The reaction started to take place immediately and the temperature rose approximately 10 to 15. Cooling water was run through the coils so that the tem: perature for addition of glycide was controlled within the. range roughly of 110 to C. The addition was continuous within limitations and all the g'lycide' was addediin less than -two hours.

This reaction took place at atmospheric pressure with simply a small stream of nitrogen passing into the autoclave at the very top and passing out I-through the openiciondenserso as to avoid any possible entrance-ofair. When the reaction was complete this condenser was shut oh :and also the opening tothe 'glycideiinlet and to the equalizing line. 'Thesequipment .was used-as an autoclave during theaddition ofpropylene oxide and ethylene oxide. .In other words, the equipment was operated under pressure. At this point addition of propylene-oxide was started. It :was added continuously atsuch speed thatit wasabsorbed by.the.reaction. asrapidly as added. The :amount of propyleneioxide added was 88 pounds. The time required .to .add this propylenecoxide wasslightly in excess of one hour, aboutlM; hours. Duringthis time the temperature was maintained at ;l5.0 .to 160 0., using cooling water through the .inner coils when necessary and otherwise applying heat if required. At the end -,of the addition of the propylene oxide there was added ethylene oxide, as previously indicated. The ;amount ofethylene oxideadded was 8Q pounds. The temperature employed, and operating conditions, were the same as with the addition of propylene oxide. It is to be noted, however, that ethylene oxide appears to be more .reactive and the reaction seems to require algreater amount of cooling water to hold the temperature range indicated. The time required to addthe ethylene oxide was about the same, or'sligh tly ,less, usually just a little more than an hour.

During the addition of the propylene and ethylene oxides, the pressure was'held at approximately 50 pounds ,per square inch gauge pressure, or less. Whenall the oxide had been added (ethylene oxide being the final addition in this particular instance) the autoclave was permitted to stay at the same temperature range for another half hour, even longer if required, or 'until thegauge pressure had been reduced to I zero or substantially 'zero, indicating the reaction was complete. "The final "product was an oily material, somewhat vi'scous-in-nature, resembling castor-oiland having a definite alphaterpineol or terpene-like-odor. -It was soluble in water and also soluble'in-non-aqueous solvents, such *as aromatic hydrocarbons, and others, although not soluble in some non-polar hydrocarbon solvents. The final yield was substantially the total weight of the initial reactants.

Example 2b The same procedure was followed as in Example lb, preceding, except-thattheodor'of addition of the oxides was reversed, the ethylene oxide being added first and the propylene oxide last. The time period, temperature range, pressure, etc., were kept the same as in Example lb, preceding.

Example 31) The same ratios were used, andthe same procedure was followed as in Example 1b, but with the following difference; the equipment was used first as an autoclave to add thegpropylene oxide.

All the propylene oxide was added, the'condenser was open to atmospheric pressure, a slow stream of nitrogen was passed through the equipment to ,prevent air from coming in contact with the reaction mass, and then the same amount of glycide was'added asin Example "1b, asthe second'alkylene oxide reactant instead of'the first.

Wheniall therglycideihadibeen added inlapproxi -T mately a 2-hour :period :of :time, Jthe connections were changed so that "-the ethylene oxide :was added. The amounts employed, operating conditions, etc., were the same as in Example 1b.

' Example 4b The same procedure was followed as in Example :3b, preceding, except ithat the stages LOf addition ofethylene oxide and propylene .-joxid'e were reversed, that is, the ethylene oxide was addedas the first stage, usingi'the equipment-218s an autoclave, then theglyci'de wasadded, and then .the propyleneoxide. The amounts .used,

operating =conditions, .etc., were identically the same.as in Example .112, preceding, except for;

an autoclave, first to add the propylene oxide and then to add the ethylene oxide,and thenathe:

glycide when using the equipment with :a condenser open to the atmosphere with :a slow stream of nitrogen passing through :to prevent entrance of air.

Example "617 The product obtained ,from Example 2 11. in Part 2, preceding, was treated with 7.5 pounds of glycide-in the manner described in'Example 'l'b, preceding. It isto be-noted that-this example againis simply a :variation of Example lbgin which the ethyleneoxide wasadded first-and then .the propylene oxide. During .these two additions the equipment was .used as an autoclave and then the customary .Jchange made-and glycide added to the extent 'of'7.5 pounds-in the manner described inrExample'lb, preceding. I

Example "7b a .The same procedure"wasfollowedrasin .Exam After the. lycidewas added .the propyleneioxide and 'ethyl-' ple 1b with the following change.

ene oxide-were added as amixture (l68 pounds)... This mixture of ethylene .oxideand propylene oxide was obtained from88 pounds of propylene oxide and pounds of ethylene oxide. In this instanceagain, the time range, temperature, and. pressures were kept substantially the same as'in .Example 11b, preceding.

Example 811 The product obtained from Example 342 described in'Part 2, preceding, was treated with '715 pounds of glycide in the 'mannerpreviously described under the heading of Example lb? This is in essence simply a variation of Example 71) in which the mixed ethylene oxide and-propyl-5 ene oxide are added, using the equipment first as an autoclave, and then the glycide is addedsubsequently in the customary manner as described.

Example 9b The examples previously described 'as Examples 1b, through 81), inclusive, were repeated makingthe following change. The amount of catalyst added, instead "of "being 12.5 ounces "was increased to 14 ounces. The amount of glycide used,-instead"of being 755 pounds was-increased to previously The amounts of ethylene oxide and propylene oxide and terpineol were kept constant.

Example b The same procedure as in Example 1b, preceding, was conducted on a laboratory scale 10 employing a small autoclave having a capacity of approximately one liter, or up to a 5-gallon size. The amount of alpha-terpineol employed was 46.2 grams, the amount'of glycide employed was 22.5 grams, the amount of propylene oxide employed was 260 grams, and the amount of ethylene oxide employed was 240 grams. The amount of caustic soda used as a catalyst was 2.4 grams.

The operating conditions were substantially the same as on a larger scale. Actually the reaction seemed to go fasterin the small autoclave and the time of absorption could be reduced, if desired. In many instances absorption would take place in the laboratory autoclave in a fraction of the time required in the larger autoclave; in fact, in many instances, absorption was complete in 5 to 10 or 15 minutes, as compared to one hour on a larger scale. Needless to say, on a large scale, addition must be conducted carefully because there is an obvious hazard in handling 3 a large quantity of material in an autoclave which is not necessarily present in the use of a small vessel.

Example 11b The examples conducted on a large scale in Examples 2b to 9b, inclusive, were repeated on a small scale, using the same amount of the ingredients above indicated, except in the subsequent experiments where twice as much glycide was employed, and in such instances the amount of glycide was 45 grams instead of 22 grams, and the amount of catalyst used with this larger amount of glycide was 2.75 grams. Inall other respects all the variants were conducted in the same manner as previously described except that oxyethylation and oxypropylation took place much more rapidly, frequently in a matter of minutes as indicated, and the addition of glycide took place in less time, requirin 15 minutes to 50 approximately 50 minutes.

as described in Examples 10b and 1112. They amount of ethylene oxide was equal to the terpineol in a molal ratio or else two moles were employed for each mole of terpineol. In the preparation of these compounds the alkaline catalyst was either flake caustic soda finely ground with mortar and pestle, or powdered sodium methylate equivalent to 6.7% of the terpineol employed. In these experiments the glycide was added at three difierent points and reacted immediately with terpineol; or the terpineol was reacted with propylene oxide and then with glycide, and then with ethylene oxide; or the terpineol was reacted with propylene oxide, eth-' ylene oxide and glycide. Needless to say, hundreds of variants within the specification of the invention are possible. Not all could be prepared. A number of those prepared are indicated in the table which appears in Part2. All the experiments in which the proportion of the reactants corresponded to Example A in Part 2 bear the same A indication, for instance, AA. Those which correspond to B, bear the same B indication, for instance, BBB. The table immediately preceding shows the order in which the reactants were added to the terpineol. On the lefthand side are those prepared using one mole of glycide for each mole of terpineol. On the righthand side are included experiments where two moles of glycide were used, and the Figure 2 precedes the letters AA, BBB, CCCC, etc. As indicated in this table, spot checks were made across the board insofar that it would have been impossible to prepare all the possible modifications.

Incidentally, the physical appearance of the materials obtained using glycide in addition to ethylene oxide and propylene oxide is substan-v tially the same as those obtained in which glycide isnot used. There is no marked difierence in physical appearance and glycide does, of course, add a greater proportion of water solubility. Needless to say, visual examination, or simple physical tests do not reveal the difierences in structure pointed out in Part 1. These polyglycol ethers are comparatively thin liquids, sometimes showing only modest viscosity, and the color varies from almost water-White to pale amber. The color seems to be due to impuritiesand is a trace of iron getting into the compound I Glycide equal to mol to mol of Glycide equal to 2 moles per mol of terpineol terpineol Reactants Other than Glycide as reported in table in Part Two for Ex. No. Glycide (1) PM) (1) PrO (l) Glycide (1) PrO (1) H0 (1) PrO (2) G1yc1de(2) EtO (2) PrO (2) Glycide (2) EtO (2) EtO (3) EtO (3) G1ycide(3) EtO (3) B (3) Glycide (3) AA 2AA BBB 2BBB 0000 20000 DD 2DD EEE 2EEE FFFF 2FFFF GG 2GG HHH 2111111 1111 21H! .lJ 2H 7 KKK 2KKK LLLL 2LLLL MM 2MM NNN 2NNN 0000 20000 PP QQQ ZPP QQQ RRRR 2RRRR SS 2S8 See the table which appears in Part 2, preceding. This same series of experiments were re- Heated. usingth a e ent nd u e during the process of manufacture, or may be present in the catalyst. The products, of course,

I show a considerable range of insolubility, from 5.25 a stage where they are dispersible or miscible, to products which, at least in dilute solution, have an apparently homogeneous or transparent appearance. The odor, if any, is generally sugges- 26 ience, referring to the table which includes A through S in Part 2, it is to be noted that the initial mixtureemploys 15 parts of terpineol, 45 parts of propylene-oxide, and 40 parts of ethyltive of a terpene or similar product. ene oxide. In the second example there are em- PART 4 played. 1011915355, terpineol, 40. parts. ethylene oxide, and'50 partsgpropylene oxide. The table Referring to Figure 3, it is apparent that alshows the mixture with the three-component though a number of examples have been included, constituent (when recalculated back to. 100% and particular reference is made to Examples A 10,. basis) and the corresponding figure when 1% to through S, that there is a limit to the numbers 25% glycideisjpresent. The tables are self-exwhich can be included without producing d'eplanatory and illustratecompositions which set scription which becomes burdensome in length. the boundary or limiting compositions. We have This applies to an even greater degree to the fourspot. checked such compositions and prepared a component system for the reason that one has 15 substantial'number but: are. not including them included all points within the truncated-tetra for the reason'that such inclusionwould be-only hedral pyramid depicted in Figure 4 anddefinedi. repetitious over and above What has been said by E. F, G, H-I, J, K, L. However, for conven-- previously. 1

. TableA TABLE FOR EX.,'A SERIES-POINT 1 ON TRIANGULARI GRAPH-'- (Figure 3) 1 Per Cent Remaining? Regg gg g gg g gg g gg: actants Calculated Back: Per Cent. gulal. Gm h to Allow for Per.- Cent; PnOent Remaining P Glycid,

Glycid 1 3 React,

ants Al 11 T i .41 h T p 3 .er- 1 p a erp EEtO .PrO. pineol EtO PrO 7- 93- 15- 40. 45.. 13-9- 37.2 41.9 3 92 15 40 45 13. 3 35. 3 41.4 9 91 15 40 45 13. 5 35. 4 41. 0 10 90 40 45 13. 5 35. 0 40. 5 11 39 15 40 45 13.3 35. 5 40. 1 12 33 15 40 45 13. 2 35. 2 39. 5 13 37 15 40 45 13. o 34. 3 39. 2 14 35 15 40. 45 12.9 34.4 33.7 15 35 15 I 40 45 12.7 34.0 33.3 15 34 15 40 45 12. 5 33. 5 37.3 17 33 15 40 45 12. 4 33. 2 37. 4 13 I 32 15 40 45 12.3 32.3 35.9 19 31 15a 40 45. 12.1 32.4 35.5: 20 15 401 45 12.0 32.0 35.0 21 79 15 11.3 31. 5 35. 5 22 73 15 40 45 11. 7 31.2 35. 1 23 77. 15.. 40 45. 11. 5, 30. 3 3 7 24 75 15 40 45 11. 4 30. 4 34. 2 25' 75 15 4o 45 11.2 30.4 33. 3

TableB TABLE FOR EX. B. SERIES-POINT 2 ON TRIANGULAR GRAPH- (Flgure 3) Per Cent Remaining 3 Re- P318331; fig fg g 5 3 actants Calculated Back "Per Cent; ulgrGra h n r to Allow iorPer Gent. Per Cent: Remaining g p Glycid Glycid 3 Reactants AI h T A1 11 T I p 3 erp 3 erpineol Eto Pro pineol Eto O 1 99 10 40 9. 9 39. 5 '49. 5 2 93 10 40' 50 9.3 39.2 49.0 3 97 10 40 50 9.7 33.3 43.5 4 95 10 40' 50 9.5 33.4 43.0 5 95 10 40' 50 9.5 33.0 47.5 5 94 10 I 40 50 9.4 37.5 47.0 7 93 10 40 50 9.3 37.2 45.5 1 3 92 10 1 40 50 9.2 35.3 45.0 9 91 10 1 40 50 9.1 35.4 45.5 10 90 10 1 40 50 9.0 35.0 45.0 1 11 39 10 40 50 3.9 35.5 44.5 12 33 10 40. 50 3.3 35.2 -44.0 13 37 10 40: 50 3.7 34.3 43.5 14 35 10 40 50 3.5 34.4 3.0 I 15 35 10 1 40. 50 3.5 34.0 425. 15 34 10 1 40' 50 3.4 33.5 42.0 1 17 83.. .10. z 0 0 -3.. 3 Al- 13 32 10 40 50 3. 2 32. 3 41 19 31 10 40 50 3. 1 32. 4 40. 5 20 30 10 40 50 3. 0 32. 0 40. 0 21 79 10 40 50 7. 9 31. 5 39. 5 22 73 10 40 50 7. 3 31.2 39. 0 23 77 10 40 50 7. 7' 30. 3 33. 5 24 75 10 40 50 7. 5 30. 4 33. 0 25 75 10 40 50 7. 5 30. 0 37. 5

PrO

PrO

EtO

ELO

Per Cent Remaining 3 Reactants Calculated Back to Allow for Per Cent Glycid pineol Per Cent Remaining 3 Reactants Calculated Back to Allow for Per Cent Glycld pmeol Pro AlpllaTer- Pro AlpllaTer (Figure 3) EtO Table D (Figure 3) EtO Ta ble c O SERIES-POINT 3 ON TRIANGULAR GRAPH- Per Cent Remaining 3 Re actants Based on Triangular Graph Alpha Terpineol Per Cent Remaining 3 Reactants Based on Triangulal Graph Alpha Terplneol Per Cent 3 Reactants Per Cent 3 Reach ants 7 5 12 1234.3 muummlmnmmmzzww Per Cent Remaining Glycid Per Cent Remaining Glycld TABLE FOR EX. D QERIEB-POINT 4 ON TRIANGULAR GRAPH- TABLE FOR EX.

1 12 5 m1mmmmmummmzzwuz a o wuso ULAR GRAPH- Per Cent Remaining} Reactants Calculated Back to, AlIow'forrBer' Gent" Glycid' pineal Per Cent Remaining} Reactants Calculated Back to-lA llowforl Per Gent- Glycid pineol Pro Alpha. Ten

ON TRIANGULAR GRAPH- Pro AlphaTgr- Table E i u e 3) EtO Table F i ure E I; O

Per Cent Remaining 3 Reactants Based on Triangular Graph pineol Alpha Ter- Per Cent Remaining 3 Reactants Based on Triangular Graph Alpha Terpineol Per Cent 3 Reactants Per Cent 3 Reactants Per Cent Remainjn Glyeid TABLE FOR EX. E SERIES-POINT 5 ON TRIANG Per Cent Remainin Glycld TABLE FOR EX. F SERIES-POINT 6 1 5 gwmnmmummnmmmzmwmz TABLE FOR EX. G SERIES-a8 Table G'- INT 7 ON TRIANGULAR GRAPH- TABLE FOR EX. H SERIES-POINT 8 ON TRIANGULAR GRAPH- (Figure 3) gure 3) Per Cent Remaining 3 Reg gg g gg g fi rflgg: actaut-s Calculated Back Per Cent gular Gm h to Allow for Per Cent Per Cent Remaining p Glycid Glyeld 3 Reactants Al 11 T A1 h 'I p a. er- 1) 2. erpmeol EtO PrO pineal EtO PrO 1 99 8. 45 44. 47. 55 8. 36 43. 6 47. 04 2 98 8. 45 44. O 47. 55 8. 28 43. 2 46. 52 3 97 8. 45 44. 0 47. 55 8. 20 42. 7 46. 10 4 96 8. 45 44. O 47. 55 8. 12 42. 2 45. 68 5 95 8. 45 44. 0 47. 55 8. 04 41. 8 45. 16 6 94 8. 45 44. 0 47. 55 7. 94 41. 3 44. 76 7 93 8. 45 44. 0 47. 55 7. 86 40. 9 44. 24 8 92 8. 45 44. 0 47. 55 7. 78 40. 5 43. 72 9 91 8. 45 44. 0 47. 55 7. 70 40. 0 43. 30 10 9O 8. 45 44. 0 47. 55 7. 62 39. 6 42. 78 11 89 8. 45 44. 0 47. 55 7. 53 39. 2 42. 27 12 88 8. 45 44. 0 47. 55 7. 44 38. 7 41. 86 13 87 8. 45 44. 0 47. 55 7. 36 38. 3 41. 34 14 86 8. 45 44. 0 47. 55 7. 27 37. 8 40. 93 15 85 8. 45 44. O 47. 55 7. 18 37. 4 40. 42 16 84 8. 45 44. 0 47. 55 7. 10 37. 0 39. 90 17 83 8. 45 44. 0 47. 55 7. O2 36. 5 39. 48 18 82 8. 45 44. 0 47. 55 6. 94 36. 1 38. 96 19 81 8. 45 44. 0 47. 55 6. 85 35. 7 38. 45 20 80 8. 45 44. O 47. 55 6. 76 35. 2 38. 04 21 79 8. 45 44. 0 47. 55 6. 68 34. 8 37. 52 22 78 8. 45 44. 0 47. 55 6. 59 34. 3 37. 11 23 77 8. 45 44. 0 47. 55 6. 51 33. 8 36. 69 24 76 8. 45 44. 0 47. 55 6. 43 I 33. 3 36. 27 75 8. 45 44. 0 47. 6. 34 33. 0 35. 66

Table H Per Cent Remaining 3 Reg gg g gg ga gg g gg: actants Calculated Back Per Cent Gm h to Allow for Per Cent Per Cent Remaining gu p Glycid Glycid 3 React- Bnts A1 h T Al 11 'I p a erp 9. er-

pineol EtO PrO pineol EtO PrO 1 99 20 54 26 19. 8 53. 4 25. 8 2 98 2O 54 26 19. 6 53. 1 25. 5 3 97 20 54 26 19. 4 52. 4 25. 2 4 96 20 54 26 19. 2 51. 8 25. 0 5 95 20 54 26 19. 0 51. 3 24. 7 6 94 20 54 26 18. 8 50. 8 24. 4 7 93 20 54 26 18. 6 50. 2 24. 2 8 92 20 54 26 18. 4 49. 7 23. 9 9 91 20 54 26 18. 2 49. 2 23. 6 1O 90 20 54 26 18. 0 48. 6 23. 4 11 89 20 54 26 17. 8 48. 1 23. 1 12 88 20 54 26 17. 6 47. 5 22. 8 13 87 20 54 26 17. 4 47. 22. 6 14 S6 20 54 26 17. 2 46. 5 22. 3 15 85 20 54 26 17. 0 45. 9 22. 1 16 84 20 54 26 16. 8 45. 3 2l. 8 17 83 20 54 26 16. 6 44.8 21.6 18 82 20 54 26 16. 4 44. 2 21. 3 19 81 20 54 26 16. 2 43. 7 21. 1 20 80 20 54 26 16. 0 43. 2 20. 8 21 79 20 54 26 15. 8 42. 7 20. 5 22 78 20 54 26 15. 6 42. 1 20. 3 23 77 20 54 26 15. 4 41. 6 20. 0 24 76 20 54 26 15.2 41. 1 19. 7 2E 20 54 26 15. 0 40. 5 19. 5

Table K TABLE FOR EX. K SERIESPOINT 11 ON TRIANGULAR GRAPH- (Flgure 3) Per Cent Rem dining 3 Re- Per g3: %g g g ggj actants Calculated Back Per Cent ac lar Gm 1 to Allow for Per Cent Per Cent Remaining gu p Glycid Glycid 3 Reactants A1 11 T A1 11 T p a erp a erpmeol EtO PrO pineol EtO PrO 1 99 2O 2O 6O 19. 8 19. 8 59. 4 2 98 20 20 60 19. 6 19. 6 58. 8 3 97 20 20 60 19. 4 19. 4 58. 2 4 96 20 20 60 19. 2 19. 2 57. 6 5 95 20 2O 60 19. 19. 0 57. 0 6 94 20 2O 60 18. 8, 18. 56. 4 7 93 20 20 60 18. 6 18- 6 55. 8 8 92 20 20 6O 18. 4 18. 4 55. 2 9 91 20 2O 60 18. 2 18. 2 54. 6 10 9U 20 2O 60 18. 0 18. 0 54. 0 11. 89 2O 20 60 17. 8 17. 8 53. 4 12 88 2O 20 60 17. 6 17. 6 52. 8 13 87 20 2O 60 17. 4 17. 4 52. 2 14 86 20 20 60 17. 2 17. 2 51. 6 15 85 20 60 17. 0 17. 0 51. 0 16 84 20 20 60 16. 8 16. 8 50. 4 17 83 20 2O 60 16. 6 16. 6 49. 8 18 82 20 20 60 16. 4 16. 4 49. 2 19 81 20 20 60 16. 2 16. 2 48. 6 20 80 20 20 6O 16. 0 16. 0 48. 0 21 79 20 20 60 15. 8 15. 8 47. 4 22 78 20 2O 60 15. 6 15. 6 46. 8 23 77 20 2O 60 15. 4 15. 4 46. 2 24 76 20 20 6O 15. 2 l5. 2 45. G 25 75 20 20 60 15. O 15. 0 45. 0

PART 5 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent,

such as water, petroleum hydrocarbons, such as' our process may be admixed with one or more ofv the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

type of material, either as such or in the form of derivatives, will ultimately be employed in no less than of all chemical demulsifying agents used throughout the world.

- In practicing our process for resolving petroalone or in combination with other demulsifying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in a tank and conduct a batch treatment type of demulsification procedure to recover clean oil. In this procedure the emulsion "is admixed with the demulsifier, for example by It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of l to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000 or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

The present invention is concerned With treatcases mixing is achieved by heating the emulsion 7 while dripping in the demulsifier, depending upon agitating the tank of emulsion and slowly dripping demulsifier into the emulsion. In some the convection currents in the emulsion to produce satisfactory admixture. In a third modification of this type of treatment, a circulating pump withdraws emulsion from, 9. g., the bottom- 7 of the tank, and re-introduces it into the top of the tank, the demulsifier being added, forexment of petroleum emulsions by means of certain oxyalkylated resins which are hydrophile or sub- "j Such resins in turn surfaceor surface-active. are oxyalkylation-susceptible, water-insoluble, organic solvent-soluble, fusible phenolaldehyde resins, derived from difunctional phenols having a 2,4,6 hydrocarbon substituent with 4 to 8 carbon atoms. Based on actual large scale application in a large number of oil fields in the United States and certain foreign countries, we believe that this ample, at the suction side of said circulating pump.

In a second type of treating procedure, the demulsifier is introduced into the well fluids at the well-head or at some point between the well-head and the final oil storage tank, by means of an adjustable proportioning mechanism or proportioning pump. Ordinarily the ifiow of fluids through .the subsequent lines and fitting sufiices to pro-' duce the desired degree of mixingor demulsifier and emulsion, although in som instances additional mixing devices may be introduced into the flow system. In this general procedure, the system may include various mechanical devices for withdrawing free water, separating entrained water, or accomplishing quiescent settling of the 

1. A PROCESS FOR BREAKING PETROLEUM EMUSLIONS OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING AT LEAST ONE COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF ALPHATERPINEOL; SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM ALPHA-TERPINEOL, GLYCIDE, ETHYLENE OXIDE AND PROPYLENE OXIDE IN SUCH WEIGHT PROPORTIONS SO THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURE STATED IN TERMS OF INITIAL REACTANTS LIES APPROXIMATELY WITHIN THE TRUNCATED TRAPEZOIDAL PYRAMID IDENTIFIED AS E,F,G,H-I, J,K,L IN FIGURE 4, WITH THE PROVISO THAT THE PERCENTAGE OF GLYCIDES IS WITHIN THE LIMITS OF 2% TO 25% BY WEIGHT AND THAT THE REMAINING THREE INITIAL REACTANTS, RECALCULATED TO A 100% BASIS, LIE APPROXIMATELY WITHIN THE TRAPEZOIDAL AREA DEFINED APPROXIMATELY IN FIGURE 3 BY POINTS 8,9, 10 AND
 11. 